NO300015B1 - Solid catalyst component in a polymerization catalyst, process for preparing such component and use thereof - Google Patents

Abstract

Disclosed is a polymetallic supported catalyst component comprising an activated anhydrous MgCl2 solid support which has been treated with at least one treatment of at least two halogen-containing transition metal compounds, wherein one is a halogen-containing titanium metal compound and one is a halogen-containing non-titanium transition metal compound, optionally, in the presence of an electron donor and the processes for producing the component. A catalyst for the polymerization of at least one alpha-olefin of the formula CH2=CHR, where R is H or a C1-12 branched or straight chain alkyl or substituted or unsubstituted cycloalkyl, by reacting this supported catalyst component with an organometallic cocatalyst, optionally in the presence of an electron donor, and the polymerization of at least one alpha-olefin with the catalyst are also disclosed. The resulting Polymers, particularly propylene polymers, have a controllable atactic content, which is expressed herein in terms of its xylene solubility at room temperature (XSRT), wherein the ratio of the I.V. of the XSRT fraction to the I.V. of the bulk polymer is greater than or equal to 0.50.

Description

The present invention relates to a polymetallic supported catalyst component, a method for producing the polymetallic supported catalyst component, and the use of such a component for polymers in the form of alpha-olefins with the formula CH2=CHR where R is H or a C^-C^2 branched or straight chain alkyl or unsubstituted or substituted cycloalkyl.

The polymerization of alpha-olefins, especially propylene, with Ziegler-Natta catalysts, comprising the reaction products of organometallic compounds with transition metal compounds to produce highly crystalline, isotactic polymers, is known. The highly crystalline, isotactic fraction is typically separated from the amorphous and low molecular weight and semi-crystalline fractions by extraction with a hydrocarbon solvent, such as hexane or kerosene. Since the advent of these catalysts, research activity in this area has generally involved improving the yield, stereospecificity and morphology of the crystalline, isotactic polymers. This was achieved with the development of a highly active and strongly stereospecific catalyst system comprising TiCl4 and an electron donor compound (Lewis base) supported on an activated, anhydrous solid MgCl2 catalyst component and an organo-aluminum activator as cocatalyst, with or without an electron donor compound. The propylene homopolymers prepared with this catalyst typically have an isotacticity in excess of 95$ as determined by the number fraction of isotactic pentads from <13>C NMR analysis and a percent XRT of 2-5, where the ratio for I.V. to the entire polymer is less than 0.50. Despite the flexibility of this catalyst system, it does not yield certain soft resins that have elastic properties or allow the production of a high molecular weight atactic polymer.

US Patent 4,562,170 describes a supported catalyst component for the polymerization of alpha-olefins, particularly ethylene, which requires a metal oxide support material from the metals in groups 2a, 3a, 4a and 4b of the periodic table. The supported component is prepared under anhydrous conditions by a sequence of steps comprising forming a slurry of the metal oxide, preferably dehydrated silicon dioxide with a high surface area, adding a solution of an organomagnesium compound, adding and reacting a solution of a hafnium compound, adding and reacting of a halogenator, addition and reaction of a tetravalent titanium compound and recovery of the solid catalyst component. It is used with an organoaluminium cocatalyst in the polymerization of ethylene. A similar catalyst system is described in US patents 4,554,265 and 4,618,660 with the exception that the organomagnesium compound in a solution is first reacted with a zirconium compound in a solution instead of a hafnium compound.

US Patents 4,578,373 and 4,665,265 relate to a supported catalyst component which is quite similar to those described in US Patents 4,562,170, 4,554,265 and 4,618,660 as discussed above. The main difference seems to be that a solution of a zirconium compound, hafnium compound or mixtures thereof is used instead of the solution of a hafnium compound or a solution of a zirconium compound.

US Patents 4,310,648 and 4,356,111 describe an olefin polymerization catalyst component prepared by reacting a trivalent or tetravalent titanium compound, a zirconium compound, and an organomagnesium compound and a halogen source, such as ethylaluminum dichloride.

According to the present invention, a solid catalyst component is provided in a polymerization catalyst based on a reaction product of titanium, magnesium and halogen, which is further reacted with titanium and/or zirconium, and further with aluminum or titanium, characterized in that

the solid catalyst component essentially consists of an activated, anhydrous, solid MgClg/alcohol adduct support which

has first been treated with a combination of a halogen-containing titanium metal compound selected from titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium oxybromide and trichlorotitanium ethoxide, and at least one halogen-containing non-titanium metal selected from Hf, Zr and Sc, optionally in the presence of a polar liquid medium and an electron donor, and then treated one or more times with one of said halogen-containing titanium metal compounds, halogen-containing non-titanium metal compounds or a combination thereof, solids being isolated between said treatments.

Furthermore, a method for the production of a solid catalyst component is provided, and this method is characterized in that it essentially consists of treating an activated, anhydrous MgCl2/alcohol adduct, in an inert atmosphere, first with a combination of a halogen-containing titanium metal compound selected from titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium oxybromide and trichlorotitanium ethoxide, and at least one halogen-containing non-titanium metal selected from Hf, Zr and Sc, optionally in the presence of a polar liquid medium and of an electron donor, and then treatment one or more times with one of said halogen-containing titanium metal compound, halogen-containing non-titanium metal compound or a combination thereof, initially at 0°C and then at a temperature from 30 to 120°C for a time period from 30 to 240 minutes for each treatment, solids being isolated between treatments.

The invention also provides for the use of the solid catalyst component as defined in accompanying claims 1-4 together with an organometallic compound as an activator, optionally with an electron donor, for the polymerization of alpha-olefins. It is preferred that this application comprises the polymerization of at least one alpha-olefin monomer of the formula CH2=CHR where R is a C1-C^2 branched or straight chain alkyl or unsubstituted or substituted cycloalkyl in the presence of an inert hydride carbon solvent and the catalyst component according to claim 2 at a temperature in the range 50-80°C for 1-4 hours, and recovery of the resulting polymer.

When the above-mentioned cycloalkyl group is substituted, it is preferably substituted in the 4-position. Typical sub-st in tuent groups are C^-C^3 alkyl or halide or both.

With the present catalyst component, in particular, propylene polymers can be obtained which have a controllable atactic content, which in the present context is expressed as its xylene solubility at room temperature (XSRT), and shows a ratio of the IV value of the xylene-soluble fraction to the IV value of the bulk polymer which is greater than or equal to 0.50.

The activated, anhydrous MgClg carrier can be prepared according to any of the methods described in US patents 4,544,717, 4,294,721 and 4,220,554.

Alternatively, the solid catalyst support can be prepared by forming an adduct of magnesium dichloride and an alcohol, such as ethanol, propanol, butanol, isobutanol and 2-ethylhexanol, where the molar ratio is from 1:1 to 1:3, which is then further treated according to the invention.

A magnesium dichloride/alcohol adduct containing generally 3 mol of alcohol per mol MgCl2 can be prepared by mixing the alcohol with magnesium dichlorides in an inert hydrocarbon liquid which is immiscible with the adduct, heating the mixture to the melting temperature of the adduct under vigorous stirring at 200-5000 rpm. when using e.g. of an Ultra Turrax T-45 N stirrer. The emulsion thus obtained is cooled rapidly to cause the adduct to solidify into spherical particles. The adduct particles are dried and partially dealcoholized under an inert atmosphere, such as nitrogen, by gradually increasing the temperature from 50°C to 130°C for a period of time sufficient to reduce the alcohol content from 3 mol to 1-1.5 mol per moles of MgClg. The resulting partially dealcoholated adduct is in the form of spherical particles having an average diameter of 50-350 pm, a surface area, as measured by B.E.T. when using a Sorptomatic 1800 device, from approx. 9 to 50 m^/g and a porosity, determined with a mercury porosimeter, of 0.6-2 cm<3>/g. A MgCl2.3 ROH adduct, where R is a straight or branched C2-C^q alkyl, can e.g. is prepared in accordance with the ingredients and method in example 2 in US patent 4,399,054, with the exception that the stirring is carried out at 3000 rpm. instead of 10,000 rpm. The adduct particles thus formed are recovered by filtration, washed three times at room temperature with 500 ml aliquots of anhydrous hexane and heated gradually by increasing the temperature from 50°C to 130°C under nitrogen for a period of time sufficient to reduce the alcohol content from 3 mol to approx. 1.5 mol per moles of MgC^.

The activated MgCl£ can be activated prior to treatment with the relevant halogen-containing titanium and non-titanium metal compounds or formed in situ from a precursor of the MgCl2 material under conditions which form and activate the magnesium dichloride. One such condition is the reaction of a halogen-containing titanium compound, such as titanium tetrachloride, with a Mg compound such as Mg(0Et)2 at 30-120°C with stirring, generally approx. 250 rpm. The key is the use of an activated MgCl2, not the methods for achieving this.

The solid, supported catalyst component is prepared as indicated above, with the solids being isolated between treatments and with the order of treatment with and the relative amounts of the halogen-containing titanium and non-titanium metal compounds being used to influence catalyst activity and polymer properties. The carrier is treated with a combination of the halogen-containing titanium compound and said at least one halogen-containing non-titanium metal compound first. This gives a predominantly atactic polymer, i.e. one that has a highly xylene-soluble fraction. The preferred combination is the halogen-containing titanium compound with a halogen-containing zirconium compound or a halogen-containing hafnium compound. In order to obtain a substantially isotactic polymer, i.e. one with a fraction of low xylene solubility, it is preferred to treat the support first with a halogen-containing titanium compound in the presence of an electron donor. After the first treatment, the solids are separated and re-treated one or more times with various combinations of the halogen-containing titanium and non-titanium metal compounds, the solids being isolated between treatments.

Any polar liquid medium in which the halogen-containing titanium and non-titanium metal compounds are at least sparingly soluble and the solid, activated, anhydrous MgCl 2 ~ carrier is substantially insoluble, and which is substantially inert with respect to the various components of the supported catalyst component, although reactive, may be used.

Such a solid catalyst component, when prepared from anhydrous activated MgCl2 or an unactivated precursor thereof, which has been activated, exhibits an X-ray spectrum in which the most intense diffraction line appearing in the spectrum of unactivated magnesium dichloride (with a surface area of less than 3 m< 2>/g), is absent, and in its place a broadened halogen line appears with its maximum intensity shifted relative to the position of the most intense line in the unactivated spectrum, or the most intense diffraction line has half the peak width as in the smallest is 30$ greater than that of the most intense diffraction line characteristic of the X-ray spectrum of unactivated magnesium dichloride.

When prepared from a MgCl2 • 3ROH adduct which has been dealcoholized as described above, the solid catalyst component prepared therefrom has an X-ray spectrum in which the Mg chloride reflections appear, showing a halogen with maximum intensity between the angles for 2 8 at 33.5° and 35°, and where the reflection at 2 0 at 14.95° is absent. The symbol 2 8= Bragg angle.

Scandium trichloride and scandium tribromide are typical scandium compounds useful in the preparation of the present supported component. Scandium trichloride is preferred.

The titanium compounds include, as mentioned, titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium oxybromide and trichlorotitanium ethoxide. Titanium tetrachloride is preferred.

Suitable zirconium compounds include zirconium tetrachloride, zirconium tetrabromide, zirconyl bromide and zirconyl chloride. Zirconium tetrachloride is preferred.

Typical hafnium compounds include hafnium tetrachloride, hafnium tetrabromide, hafnium oxybromide and hafnium oxychloride. The preferred hafnium compound is hafnium tetrachloride.

The amount of the titanium and non-titanium metal compounds used in the production of the present solid, supported catalyst component is 5-100 mol per mol of MgClg, preferably 10-50 mol, most preferably 10-25 mol. The ratio of Ti metal to the non-titanium metal or metals, depending on the circumstances, is typically from 10:1 to 4000:1, preferably from 250:1 to 25:1.

The titanium and non-titanium metal compounds can be used unmixed (undiluted) or in a substantially inert, polar, liquid medium. A pre-activated, anhydrous MgCl2, or a Mg compound which can form MgCl2 which is then activated by treatment with the halogen-containing titanium metal compound, at a temperature of 30-120°C, can be used. The reaction components are typically stirred at from 250 to 300 rpm. in a 1 liter container. The reaction is usually carried out over a period of time from 30 to 240 min., preferably 60-180 min., most preferably 80-100 min., for each treatment.

Typical polar liquid media useful in the preparation of the supported catalyst component include acetonitrile, methylene chloride, chlorobenzene, 1,2-dichloroethane, and mixtures of chloroform and hydrocarbon solvents. Methylene chloride and 1,2-dichloroethane are the preferred polar liquid media. When a mixture of chloroform and hydrocarbon material is used, suitable hydrocarbon materials include kerosene, n-pentane, isopentane, n-hexane, isohexane and n-heptane. Normal hexane is the preferred hydrocarbon material.

Suitable electron donors for use in the preparation of the present supported catalyst component include acid amides, acid anhydrides, ketones, aldehydes and monofunctional and difunctional organic acid esters having 2-15 carbon atoms, such as methyl acetate, ethyl acetate, vinyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl benzoate , ethyl benzoate, butyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, amyl toluate, methyl anisate, ethyl oxybenzoate, ethyl pivalate, ethyl naphthoate, dimethyl phthalate, diethyl phthalate and diisobutyl phthalate (DIBP). In addition, 1,3- and 1,4- and 1,5- and higher dieters, which can be substituted on all carbon atoms, and preferably have substitutions on at least one of the inner carbon atoms, can be used. Suitable dieters include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,3- diphenyl-1,4-diethoxy-butane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-dimethoxybutane, 2,3-bis(p-fluorophenyl)-1,4 -dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane and 2,4-diiso-propyl-1,5-dimethoxypentane. Difunctional esters, such as diisobutyl phthalate, are preferred.

The supported catalyst component produced according to the present invention is recovered and washed with several, e.g. 5-20, aliquots of a substantially inert solvent. Suitable solvents for washing the catalyst component include methylene chloride, 1,3-dichloroethane, hexane and chloroform/hexane mixtures where the amount of chloroform may be 10-75% of the mixture.

The catalyst component can be stored in a dry state or as a slurry in a suitable non-reactive atmosphere, i.e. under an inert atmosphere without exposure to heat or light, either artificial or natural, for at least 6 months up to several years.

Organometallic compounds suitable for use with the present catalyst component for polymerization of alpha-olefins include organoaluminum compounds, organogallium compounds, organotransition metal compounds, organomagnesium compounds and organozinc compounds. Alkyl aluminum compounds are generally preferred.

Triisobutylaluminum (TIBAL), diisobutylaluminum hydride (TIBAL-H), diisobutylaluminum ethoxide, triethylgallium, triethylaluminum (TEAL), triisoporopylaluminum, diisobutylzinc, diethylzinc, dialkylmagnesium, such as dimethylmagnesium and diethylmagnesium, and compounds containing two or more Al atoms bonded to each other through heteroatoms such as:

are typical metal alkyl compounds. In general, from 5 to 20 mmol of organometallic activator per 0.005-0.05 g of supported catalyst component used.

Suitable electron donors for use with the organometallic compounds are organosilane compounds having silicon(IV) as the central atom with at least two alkoxy groups attached thereto and an —OCOR, —NR2 or —R group or two of these groups which may be the same or different, bound thereto, where R is alkyl, alkenyl, aryl, arylalkyl or cycloalkyl of 1-20 carbon atoms. Such compounds are described in US patents 4,472,524, 4,522,930, 4,560,671, 4,581,342 and 4,657,882. In addition, organosilane compounds containing an Si-N bond, where the nitrogen is part of a 5-8 membered heterocyclic ring, can be used. Examples of such organosilane compounds are diphenyldimethoxysilane (DPMS), dimesityldimethoxysilane (DMMS), t-butyl(4-methoxy)piperidinyl-dimethoxysilane (TB4MS), t-butyl(2-methoxy)piperidyldimethoxysilane, isobutyl(4-methyl)piperidyldimethoxysilane, dicyclohexyldimethoxysilane, t-butyltriethoxysilane and cyclohexyltriethoxysilane. Dimesityldimethoxysilane and t-butyl-(4-methyl)piperidylmethoxysilane are preferred. A method for preparing TB4MS is described in US Serial No. 386,183, filed July 26, 1989. The remaining silanes are commercially available.

In the present catalysts the ratio Mg:Me is from 0.9 to 25.0, the ratio for M':Ti is from 0.1 to 25.0, the ratio for Al:Me is from 20 to 40,000. Me is Ti, Sc, Zr, Hf, V, Nb, Ta or combinations thereof. M' is Sc, Zr, Hf, V, Nb, Ta or combinations thereof.

Alpha-olefins that can be polymerized with the present catalyst include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, vinylcyclohexane, allylbenzene, allylcyclohexane, vinylcyclopentane or mixtures thereof. hence.

The polymerization reactions using the present catalyst are carried out in an inert atmosphere in the presence of liquid or gaseous monomers or combinations thereof and, optionally, in the presence of an inert hydrocarbon solvent, at a temperature from 30 to 100°C, preferably 50-80°C, and at a pressure from atmospheric pressure to 6,895 kPa, preferably from 137.9 to 3,447.5 kPa in liquid phase polymerization and from atmospheric pressure to 4,137 kPa in gas phase polymerization. Typical stay times are from 15 min. to 6 hours, preferably 1-4 hours.

The catalyst system, i.e. the polymetallic, supported component, the organometallic activator and the electron donor, when such is used, can be added to the polymerization reactor by means of separate devices substantially simultaneously, regardless of whether the monomer is already in the reactor, or sequentially if the monomer is added to the polymerization reactor later. It is preferred to premix the supported catalyst component and the activator before the polymerization for from 3 min. to 10 min. at ambient temperature.

The olefin monomer can be added before, with or after the addition of the catalyst system to the polymerization reactor. It is preferred to add it after the addition of the catalyst system.

Hydrogen can be added as needed as a chain transfer agent to reduce the molecular weight of the polymer.

The polymerization reactions can be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which can be carried out either batchwise or continuously.

The catalysts may be contacted in advance with small amounts of olefin monomer (prepolymerization), maintaining the catalyst in suspension in a hydrocarbon solvent and polymerizing at a temperature of 60°C or below for a time sufficient to give an amount polymer which is 0.5-3 times the weight of the catalyst.

This prepolymerization can also be carried out in liquid or gaseous monomer to, in this case, produce an amount of polymer up to 1000 times the weight of the catalyst.

Unless otherwise specified, the following analytical methods were used to characterize the supported catalyst component samples and the polymer samples.

The concentration of active metals in the supported catalyst components was determined by atomic absorption spectrophotometry using a Perkin-Elmer model 3030. To analyze for Mg, Ti, Sc and V, the samples (0.07 g ± 0.01) were hydrolyzed with 25 ml 2 N ^SO^ solution containing 0.2% HC1 calculated by weight, in a sealed container under an inert gas. The samples were filtered, and aliquots were diluted as needed based on metal concentration. The resulting aliquots were analyzed by flame AA using standard techniques as described in "Analytical Methods for Atomic Absorption Spectrophotometry", Perkin-Elmer Corp., Norwalk, CT. This same method was used for Zr and Hf with the exception that a 156 HF solution containing 0.2 wt-# Al (added as AlCl3*6 H2O) was used instead of the 2 N H2SO4 solution. ;The organic compounds in the supported catalyst component were determined by gas chromatography. The sample (0.5-1.0 g) was dissolved in 20 ml of acetone and 10 ml of an internal standard solution of 0.058-0.060 molar n-dodecane in acetone was added. When the supported catalyst component contained an electron donor, di(n-butyl) phthalate was added to the internal standard solution in an amount such that a 0.035-0.037 molar di(n-butyl) phthalate solution was formed. Then 15% NE 4 OH was added dropwise until the solution had a pH value of 7 to precipitate the metals which were removed by filtration. The filtrate was analyzed by gas chromatography using an HP-5880 gas chromatograph with FID (flame ionization detector). The column was a wide bore 0.530 ID capillary column with fused silica coated with Supel cowax 10. The intrinsic viscosity of the resulting polymers was determined in decalin at 135°C using an Ubbelohde type viscometer tube according to the method of J. H. Elliott et al., J. Applied Polymer Sci. 14, 2947-2963 (1970). The percentage xylene soluble fraction was determined by dissolving a 2 g sample in 200 ml xylene at 135°C, cooling in a constant temperature bath to 22°C and filtering through rapid filter paper. An aliquot of the filtrate was evaporated to dryness, the remainder weighed and the weight-$ soluble fraction calculated. ;Melting point and heat of fusion were determined by differential scanning calorimetry (DSC) using a DuPont 9900 controller with a DuPont 910 DSC cell. Melting data were obtained under a nitrogen atmosphere at a 20°/min. heating rate after quenching from the forge. ;A Nicolet 360 spectrometer was used to determine atactic, syndiotactic and isotactic content based on <13>C NMR pentad sequence analysis (of methyl resonances) described in J. C. Randall, "Polymer Sequence Determination" Academic Press, N.Y. (1977). ;Tensile strength was determined according to the methods in ASTM D412. A Nicolet 740 SX FT infrared spectrophotometer was used to quantify the monomers in copolymer samples. The following examples illustrate the specific embodiments of the invention. In the examples, dry and oxygen-free solvents were used. The solvents were dried by storage over activated molecular sieves or by distillation from CaHg. The transition metal compounds were used as received from the manufacturer. The electron donors were dried over activated 4Å molecular sieves, unmixed or as solutions in hexane, before use. All preparations of the solid supported catalyst component and the polymerization reactions were carried out under an inert atmosphere. ;All percentages are calculated by weight unless otherwise stated. Ambient or room temperature is approx. 25°C. ;Example 1 ;This example illustrates the supported catalyst component and a method for its production. ;To a reaction vessel equipped with a cooler, an adapter and a paddle stirrer, which had been flushed with nitrogen for approx. 15-20 min., 2.5 g (11 mmol) of ZrCl4 suspended in 50 ml of unmixed T1Cl4 (0.45 mol) were added. The slurry was then cooled in a dry ice/isopar bath to 0°C with stirring at 100 rpm. A preactivated anhydrous MgCl 2 ~ carrier (5.1 g) containing 12.5% Mg and 50% ethanol was added to the reaction vessel under inert atmosphere. After the addition of the carrier was complete, the stirring speed was increased to 250 rpm, the dry ice isopar bath was replaced with an oil bath, and the reaction temperature was raised to 100°C over 1 hour under a gentle stream of nitrogen. The reaction mixture was maintained under these conditions for 90 min. At the end of this period, the stirring was stopped, and the solids were allowed to cement for approx. 20 min. at 100°C. The supernatant liquid was removed and the solids were washed five times with 50 ml portions of methylene chloride at 30°C. The solids were then treated with 50 ml of unmixed TiCl 4 (0.45 mol) while stirring at 250 rpm. The reaction mixture was then heated with the same amount of stirring to 100°C over 1 hour under a gentle stream of nitrogen.The reaction conditions were maintained for 90 min. Stirring was then stopped and the solids were allowed to settle for about 20 min at 100°C. . The supernatant was removed. The solids were washed three times at 60°C and then three times at ambient temperature with 50 mL portions of hexane. The supported catalyst component, suspended in the final wash solution, was "transferred to a Schlenk flask. The last washing solution was decanted and the catalyst dried under a reduced pressure of approx. 63.5 cm vacuum, maintained by introducing nitrogen into the vacuum manifold, at 50°C and periodic shaking until a free-flowing powder was obtained. The catalyst component showed 11.4$ Mg, 2.3$ Ti and 20.2$ Zr by elemental analysis. ;Example 2 ;The method and components in example 1 were used with the exception that 3.4 g (11 mmol) HfCl4 was used instead of ZrCl4 - The catalyst component showed 10.7$ Mg, 2.3$ Ti and 25.2$ Hf at elemental analysis. ;Example 3 ;The method and ingredients in Example 1 were used with the exception that 1.6 g SCCI3 (11 mmol) was used instead of ZrCl4- The catalyst component showed 11.2$ Mg, 6.5$ Ti and 7.8$ Sc at elemental analysis. ;Example 4 ;The method and ingredients in example 1 were used with the exception that 1.7 g of HfCl4 (5.3 mmol) and 1.2 ZrCl4 (5.2 mmol) were used instead of 2.5 g (11 mmol) of ZrCl4 . The catalyst component showed 10.4$ Mg, 2.5$ Ti, 9.3$ Zr and 15.4$ Ef by elemental analysis. ;Example 5 ;To a reaction vessel equipped with a cooler, an adapter and a paddle stirrer, which had been flushed with nitrogen for approx. 15-20 min., unmixed TiCl4 (150 ml, 1.4 mol) was added. The TiCl 4 was then cooled in a dry ice isopar bath to 0°C with stirring at 100 rpm. A preactivated anhydrous MgCl2 carrier (15.0 g) containing 11.3$ Mg and approx. 55% ethanol was added to the reaction vessel under inert atmosphere. After the addition of the carrier was complete, the stirring speed was increased to 250 rpm, the dry ice/isopar bath was replaced with an oil bath, and the reaction temperature was raised to 100°C over 1 hour under a gentle stream of nitrogen. Unmixed diisobutyl phthalate (DIBP) (3.6 mL, 14 mmol) was added dropwise via syringe when the temperature reached 50°C. The reaction temperature was maintained at 100°C for 90 min. At the end of this period, stirring was stopped and the solids were allowed to settle at 100°C for 20 min. The supernatant liquid was removed and a slurry of ZrCl 4 (3.0 g, 13 mmol) in 1,2-dichloroethane (300 mL) was added to the resulting solids. The reaction mixture was then heated to 60°C over 30 min. under a gentle stream of nitrogen and with stirring at 250 rpm. The reaction conditions were maintained for 90 min. At the end of this period, the stirring was again stopped, and the solids were allowed to settle for approx. 20 min. at 60°C. The supernatant liquid was removed and the solids were washed 5 times at 60°C and three times at ambient temperature with 100 ml portions of 1,2-dichloroethane. The supported catalyst component was then washed twice at ambient temperature with 100 mL portions of hexane. The supported catalyst component, while suspended in the final wash solution, was transferred to a Schlenk flask. The final wash solution was decanted and the catalyst dried under a reduced pressure of 63.5 cm vacuum at 50°C and shaking periodically until a free-flowing powder was obtained. The catalyst component showed 15.6$ Mg, 1.3$ Ti, 6.4$ Zr and 6.9$ DIBP by elemental analysis. ;Example 6 ;The method and ingredients in example 5 were used with the exception that methylene chloride was used instead of 1,2-dichloroethane and 40°C was used instead of 60°C. The catalyst component showed 16.4$ Mg, 1.9$ Ti, 4.6$ Zr and 5.9$ DIBP by elemental analysis. ;Example 7 ;The procedure and ingredients of Example 5 were used with the exception that 14.8 g of a preactivated, anhydrous MgClg carrier was used instead of 15.0 g, and with the exception that 7.2 ml (27 mmol) of DIBP was used instead of 3.6 ml of DIBP. The catalyst component showed 15.8$ Mg, 2.5$ Ti, 2.4$ Zr and 8.3$ DIBP by elemental analysis. ;Example 8 ;This example illustrates another supported catalyst component according to the invention and a method for its production. ;To a container that had been flushed with argon for approx. 15-20 min., 5.2 g (22 mmol) of ZrCl4 were added. Then 50 ml (0.45 mmol) of unmixed TiCl4 was added and the container was shaken or swirled intermittently until a slurry was formed (about 5-20 min). The resulting mixture was transferred under a gentle stream of argon at 13.8-34.5 kPa to a reaction vessel fitted with a septum cap and stirring paddle, which had been flushed with argon for 15-20 min. before the transfer. The slurry was then cooled in a dry ice/isopar bath to 0°C with stirring at 200 rpm. A preactivated anhydrous MgClg carrier (5.6 g) containing 11.3$ Mg and approx. 55% ethanol was added to the reaction vessel under inert atmosphere. After the addition of the carrier was complete, the septum cap was replaced with a ground glass stopper, the stirring speed was increased to 300 rpm. and the dry ice/styrofoam bath was replaced with an oil bath. The reaction mixture was heated to 100°C over the course of one hour and then held at this temperature for 3 hours. At the end of this period, the stirring was stopped, and the solids were allowed to settle for approx. 20 min. at 100°C. The supernatant liquid was removed and 200 ml of anhydrous hexane was added. The mixture was then heated to 60°C with the stirring speed at 300 rpm. for 10 min. Stirring was then stopped, and the solids were allowed to settle for approx. 5 min. at 60°C. The supernatant was removed. The solids were washed four more times in the same manner by adding 200 ml of hexane, heating to 60°C with stirring at 300 rpm. for 10 min., stopping the stirring, and the solids were allowed to settle for approx. 5 min. at 60°C, and the supernatant was removed. The solids were then washed 5 more times in the same manner at ambient temperature. The resulting supported catalyst component was then suspended in 150 mL of hexane and transferred under a stream of argon to another reaction vessel. The hexane was removed after the solids had been allowed to settle for approx. 30 min. at ambient temperature. The catalyst component was dried at 50°C under reduced pressure at approx. 50.8 cm of vacuum, maintained by supplying argon to the vacuum manifold, until substantially all free solvent had disappeared. The pressure was then reduced to approx. 63.5 cm of vacuum, and the catalyst component was shaken periodically until a free-flowing powder was obtained. The catalyst component showed 6.0$ Mg, 5.5$ Ti, 25.9$ Zr and 54.1$ Cl by elemental analysis. ;Example 9 ;The procedure of the ingredients of Example 8 was used with the exception that 5.0 g (22 mmol) of ZrCl 4 and 4.9 g of preactivated support were used, and the resulting catalyst component was washed five times with 50 ml of anhydrous methylene chloride at 30 °C while stirring at 300 rpm. for 10 min. and re-suspended in 50 ml of anhydrous emethylene chloride. This catalyst component showed 6.7$ Mg, 6.1$ Ti, 20.2$ Zr and 54.8$ Cl by elemental analysis. ;Example 10 ;The method and components in example 8 were used with the exception that 2.5 g (11 mmol) ZrCl4 and 5.0 g of preactivated carrier were used and with the exception that the catalyst component was washed according to the method in example 9. Analysis showed that the catalyst component contained 10.1$ Mg, 5.0$ Ti, 15.6$ Zr and 56.4$ Cl. ;Example 11 ;The procedure and ingredients of Example 8 were used with the exception that 1.0 g (4.3 mmol) ZrCl4 was used instead of 5.2 g, 5.0 g of preactivated anhydrous MgCl2 carrier was used instead of 5.6 g, the reaction conditions were maintained for 90 min. instead of for 3 hours, 50 ml portions of methylene chloride were used to wash instead of 200 ml portions of anhydrous hexane, a washing temperature of 30°C was used instead of 60°C, and after the last wash at 60°C in Example 8, but before the transfer to another reaction vessel for drying, the following procedure and ingredients were used. ;A sieve of 1|.0 g ZrCl4 and 50 mL unmixed TiCl4 was added to the resulting solids after the final wash, and the reaction mixture was heated to 100°C over 1 hour under argon with stirring at 300 rpm . The reaction conditions were maintained for 90 min. Stirring was then stopped, and the solids were allowed to settle for approx. 30 min. at 100°C. The supernatant was then removed and the resulting solids were washed five times at 30°C with 50 mL portions of methylene chloride and then twice at 30°C with 50 mL portions of hexane and twice at ambient temperature with 50 mL portions of hexane before drying. The analysis showed that the catalyst component contained 11.4$ Mg, 0.9$ Ti and 15.3$ Zr. ;Example 12 ;The method and ingredients of Example 8 were used with the exception that 2.5 g (11 mmol) ZrCl4 was used instead of 5.2 g, 4.9 g of preactivated anhydrous MgClg carrier was used instead of 5.6 g, the reaction conditions were maintained for 90 min. instead for 3 hours, 50 ml portions of 1,2-dichloroethane were used for washing instead of 200 ml portions of anhydrous hexane and after the last washing at 60°C, but before transfer to another reaction vessel for drying, the following method and ingredients used. The solids were then washed once with 50 ml of hexane at 60°C in the same manner as the other washes. Unmixed TiCl 4 (50 mL) was added to the resulting solids after this final wash, and the reaction was heated to 100°C for one hour under argon with stirring at 300 rpm. The reaction conditions were maintained for 90 min. Stirring was then stopped and the solids were allowed to settle for approx. 20 min. at 100°C. The supernatant was then removed and the resulting solids were washed three times at 60°C with 50 mL portions of hexane and then three times at ambient temperature with 50 mL portions of hexane. The analysis showed that the catalyst component contained 12.4$ Mg, 1.3$ Ti and 15.5$ Zr. ;Example 13 ;The method and ingredients of Example 8 were used with the exception that no ZrCl 4 was used, 5.0 g of preactivated anhydrous MgCl 2 carrier was used instead of 5.6 g, the reaction conditions were maintained for 90 min. instead for 3 hours, and before washing, the following method and ingredients were then used. ;A slurry of 1.0 g (4.3 mmol) ZrCl4 in 100 mL 1,2-dichloroethane was added to the resulting solids, and the reaction mixture was heated to 60°C over 1 hour under argon with stirring at 300 rpm The reaction conditions were maintained for 90 min. Stirring was then stopped, and the solids were allowed to settle for approx. 20 min. at 60°C. The supernatant was then removed and the resulting solids were washed five times at 60°C, three times at ambient temperature with 50 ml portions of 1,2-dichloroethane and twice at room temperature with 50 ml hexane. The analysis showed that the catalyst component contained 13.0$ Mg, 2.5$ Ti and 9.2$ Zr. ;Example 14 ;The method and ingredients of Example 8 were used with the exception that no ZrCl 4 was used, 5.1 g of preactivated anhydrous MgCl 2 carrier was used instead of 5.6 g, the reaction conditions were maintained for 60 min. instead for 3 hours, and before washing, the following method and ingredients were then used. A slurry of 1.0 g (4.3 g mmol) ZrCl 4 in 100 mL 1,2-dichloroethane was added to the resulting solids and the reaction mixture was heated to 60°C over 30 min. under argon with stirring at 300 rpm. The reaction conditions were maintained for 60 min. Stirring was then stopped, and the solids were allowed to settle for approx. 20 min. at 60°C. The supernatant was then removed and the resulting solids were washed five times at 60°C, three times at room temperature with 50 ml portions of 1,2-dichloroethane and twice at ambient temperature with 50 ml hexane. The analysis showed that the catalyst component contained 12.6% Mg, 3.2% Ti and 10.2% Zr. ;Example 15 ;The method and components in example 5 were used with the exception that 5.0 g of preactivated MgCl2 carrier containing 12.0$ Mg and approx. 50$ EtOH was used instead of 15.0 g MgCl2 ~ carrier containing 11.3$ Mg and approx. 55$ ethanol, 50 ml (0.45 mol) TiCl4 was used instead of 150 ml, and 1.2 ml (4.5 mmol) SIBP was used instead of 3.6 ml before the first solids separation and a mixture of 0.5 g (2.2 mmol) ZrCl4 and 0.7 g (2.2 mmol) HfCl4 in 100 mL 1,2-dichloroethane were added to the resulting solids instead of the slurry of 3.0 g ZrCl4 in 300 mL 1,2- dichloroethane and 50 ml wash volumes (instead of 100 ml) were used. The analysis showed that the catalyst component contained 15.8$ Mg, 1.3$ Ti, 3.3$ Hf, 4.2$ Zr and 5.4$ DIBP. ;Example 16 ;The procedure and ingredients of Example 8 were used with the exception that no ZrCl4 was used, 5.0 g of preactivated anhydrous MgC^-hairs were used instead of 5.6 g, 100 ml of TiCl4 were used instead of 50 ml, the reaction conditions were maintained for 90 min. instead for 3 hours, and before washing, the following method and ingredients were then used. A slurry of 1.0 g (4.3 mmol) ZrCl 4 in 100 mL 1,2-dichloroethane was added to the resulting solids and the reaction mixture was heated to 60°C over 30 min. under nitrogen with stirring at 250 rpm. The reaction conditions were maintained for 90 min. Stirring was then stopped, and the solids were allowed to settle for approx. 20 min. at 60°C. The supernatant was then removed and the solids were treated with ZrCl 4 again in exactly the same way. The supernatant was then removed and the resulting solids were washed five times at 60°C, three times at ambient temperature with 50 ml portions of 1,2-dichloroethane and twice at room temperature with 50 ml hexane. The analysis showed that the catalyst component contained 12.3$ Mg, 0.6 Ti and 16.4$ Zr. ;Example 17 ;The procedure and ingredients in Example 1 were used with the exception that 4.9 g of preactivated anhydrous MgClg carrier was used instead of 5.1 g, 3.4 g (11 mmol) of HfCl4 was used instead of ZrCl4, 100 ml ( 0.90 mmol) TiCl4 was used instead of 50 ml throughout, and the first solids isolated were not washed before the second treatment, and after the second treatment, but before drying, the solids were washed five times at 60° C and five times with recirculation well see temperaur with hexane (instead of three times at each temperature). The catalyst component showed 9.4$ Mg, 2.2$ Ti and 26.8$ Hf by elemental analysis. ;Example 18 ;The method and ingredients of Example 1 were used with the exception that 1.2 g (5.1 mmol) ZrCl4 was used instead of 2.5 g, the first solids were not washed, and then the following method and ingredients were used. A slurry of 1.7 g (5.3 mmol) HfCl 4 in 50 mL 1,2-dichloroethane was added to the resulting solids and the reaction mixture was heated to 60°C over 30 min. under nitrogen with stirring at 250 rpm. The reaction conditions were maintained for 90 min. Stirring was then stopped, and the solids were allowed to settle for approx. 20 min. at 60°C. The supernatant was then removed and the resulting solids were washed five times at 60°C and three times at room temperature with 50 ml portions of 1,2-dichloroethane and then twice at room temperature with 50 ml portions of 1,2-dichloroethane and then twice at room temperature with 50 ml portions of hexane. The supported catalyst component, while suspended in the final wash solution, was transferred to a Schlenk flask and dried in the usual manner. The catalyst component showed 11.6$ Mg, 1.2$ Ti, 8.5$ Zr and 11.2$ Hf by elemental analysis. ;Example 19 ;The procedure and ingredients in Example 8 were used with the exception that a slurry of 2.5 g (11 mmol) ZrCl4 in 100 ml 1,2-dichloroethane was used instead of 5.2 g ZrCl4 and 50 ml unmixed TiCl4 in the first treatment, 5.1 g of preactivated anhydrous MgCl2 support was used instead of 5.6 g, the reaction mixture was heated to 60°C for 1 hour instead of 100°C and maintained at this temperature instead for 3 hours, the solids was allowed to settle at 60°C instead of 100°C, the supernatant was removed and the resulting solids were washed five times at 60°C with 50 ml portions of 1,2-dichloroethane and then twice at 60°C with 50 ml portions of hexane , and after the last wash at 60°C in example 8, but before the room temperature washes and transfer to another reaction vessel for drying, the following method and ingredients were used. The resulting solids were treated with 50 mL (0.45 mmol) of neat CiCl 4 and the reaction mixture was heated to 100°C over 1 hour under a gentle stream of argon with stirring at 300 rpm. The reaction conditions were maintained for 90 min. Stirring was then stopped, and the solids were allowed to settle for approx. 20 min. at 100°C. The supernatant was then removed and the resulting solids were washed five times at 60°C, five times at ambient temperature with 50 mL portions of hexane. The analysis showed that the catalyst component contained 11.8$ Mg, 3.4$ Ti and 16.0$ Zr. ;Polymer! the batches of catalysts in Examples 1-7, 15 and 17 were carried out in a 3.8 liter stirred batch reactor which had been flushed for 1 hour with hot argon, cooled and then flushed with propylene gas. Using standard Schlenk techniques, 0.01-0.03 g of solid catalyst component and 6.7 mmol of the activator were premixed for 5 min. under an inert atmosphere in 50-75 ml of hexane and fed to the reactor. When an electron donor was used with the activator, it was premixed with the activator for 5 min. before mixing with the solid catalyst component. The ratio of aluminum to electron donor was varied from 20-80:1 when the donor was used. Liquid propylene, 2.2 L, was then added to the reactor. When hydrogen was used, it was added to the reactor in an amount that was necessary to reduce the molecular weight to the desired range, and the reactor was heated to 50-80°C within 5 minutes. The temperature was maintained for 2 hours. The reactor was then vented and flushed with argon. The polymer was removed and dried at 80°C under vacuum for 2 hours. If necessary, the polymer was frozen in liquid nitrogen and then ground to an average particle size of approx. 1 mm before analysis. The relevant conditions, ingredients and analytical results are set out in table 1 below. ;Example 20 ;The catalyst component in example 2 was used, and the polymerization method in examples 1-7, 15 and 17 was used with the exception that 33 g (0.58 mol ) 1-butene was added to the reactor after the liquid propylene had been added, but before heating to the reaction temperature used. The resulting copolymer had a Tm of 145°C and an AHf of 15 J/g both determined by DSC, and ca. 2.6$ butene by <13>C NMR. ;Example 21 ;The catalyst component in example 2 was used, and the polymer synthesis method for examples 1-7, 15 and 17 was used with the exception that approx. 100 g of ethylene was added incrementally throughout the polymerization reaction, the start being made after heating the contents to the reaction temperature used. The resulting copolymer had no observed Tm from 40 to 200°C by DSC, and ca. 15$ ethylene by <13>C NMR. ;Example 22 ;The catalyst component in example 2 was used with 10 mmol TIBAL activator, and the polymerization method for examples 1-7, 15 and 17 was used with the exception that 2.0 1 isobutane was used as diluent instead of 2.2 1 liquid propylene , the reaction temperature was maintained for 3 hours instead of 2 hours, and ethylene was added starting before heating and continuously thereafter to maintain the pressure at approx. 2068.5 kPa. ;The other relevant conditions, ingredients and analytical results for Examples 20-22 are set forth in Table I below. The polymers and copolymers prepared in the absence of an electron donor in the solid catalyst component, with the exception of polyethylene, are soft or rubbery polymers having 1) a room temperature xylene soluble fraction from 50 to 90$, 2) an intrinsic viscosity from above 1.0 to 6.0 in the absence of a chain transfer agent, 3) a polymer melting point (Tm), by observation, of from 140 to 160°C, determined by DSC, and 4) a crystallinity measured by heat of fusion (AHf) which varies inversely and linearly with percent XSRT and is typically from 13 to 28. The catalyst yield is from 9000 to 60,000 g polymer/g catalyst in a 2-3 hour polymerization -reaction. The polyethylene produced using the catalyst component according to the invention shows an I.V. value of approx. 20 or less depending on whether a chain transfer agent was used, and when such was used, on the amount of chain transfer agent used. Furthermore, the polyethylene produced using the present catalyst component exhibits a broad molecular weight distribution, typically wider than that of a polyethylene produced with a solid magnesium chloride-supported titanium tetrachloride catalyst component/organoaluminum compound co-catalyst system. ;The polymers and copolymers prepared using the present catalyst component having an electron donor have 1) a xylene-soluble fraction from 5 to 60$, 2) an I.V. value from 2 to 10 in the absence of a chain transfer agent, show 3) a reduced heat of fusion measured by DSC, relative to highly isotactic polymers, and shows 4) a relationship for I.V. to the XSRT fraction of I.V. for the entire polymer greater than or equal to 0.50. The crystallinity from heat of fusion (AHf), measured by DSC, is lower for the polymers prepared with an electron donor solid catalyst component (typically 20-90 J/g) than for the isotactic or copolymers prepared using a solid catalyst component comprising a halogen-containing titanium compound and electron donor supported on an activated magnesium dihalide, especially magnesium dichloride, together with a trialkyl aluminum activator and electron donor as cocatalyst (typically 100 J/g). Generally, the polymers and copolymers produced have regulated tacticity, which is shown by their xylene-soluble fractions at room temperature, and shows a ratio of I.V. to the XSRT fraction of I.V. for the entire polymer greater than or equal to 0.50. In addition, the propylene polymers having a high percentage of XSRT typically exhibit a ratio of the I.V. value to the XSRT fraction of the I.V. for the entire polymer that is greater than or equal to 0.70 and has improved properties for elongation at break and stiffening when stretched ("tension set") compared to commercially available isotactic polymers. Furthermore, the present polymers have a higher I.V. value than commercially available atactic polymers, which are waxy, solid polymers of low molecular weight that have an I.V. value of less than 0.5 and are generally used as an adhesive layer in multilayer structures.;The prepared polymers are further characterized by an isotacticity of from 45 to approx. 85$ determined by the number fraction of isotactic pentads from <*3>C NMR analysis and a melting point of 140-160°C.

The polymers can be used for the production of uniaxial and biaxial films; fibers; injection and compression molded items and extruded items. They can also be used in fabric and extrusion coating applications and in hot melt adhesives.

The polymers can be mixed with one or more fillers, such as alumina trihydrate, talc, calcium carbonate, wollastonite (CaSiOs), mica, metal flakes, glass flakes, painted glass, glass spheres, glass fibers, carbon fibers, metal fibers and aramid fibers. When fillers are present, they are typically present in an amount totaling from 1 to 40% by weight of the polymer material.

Conventional additives, such as stabilizers and pigments, may also be present. Antioxidant type stabilizers may be present in an amount from 0.05 to 1.0 pph (parts per 100), based on the weight of the polymer material. Acid neutralizing agents, if used, are typically present in an amount of from 0.05 to 0.5 pph, preferably from 0.05 to 0.2 pph, based on the weight of the polymer material. Heat stabilizers can be used in an amount from 0.05 to 1 pph, based on the weight of the polymer material. Pigments can be used in an amount from 0.2 to 5, preferably from 2 to 3 pph, based on the weight of the polymer material.

Typical antioxidants include hindered phenolic compounds such as tetrakis[methylene)-3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate)]methane. Such antacids include alkali and alkaline earth metal stearates such as sodium stearate and calcium stearate. Thioesters such as trilauryltrithiophosphate (TLTTP) and distearylthiodipropionate (DSTDP) are typical heat stabilizers. Suitable pigments include carbon black and titanium dioxide.

Claims (10)

1. Solid catalyst component in a polymerization catalyst based on a reaction product of titanium, magnesium and halogen, which is further reacted with titanium and/or zirconium, and further with aluminum or titanium, characterized in that the solid catalyst component essentially consists of an activated, anhydrous , solid MgCl2/alcohol adduct support which has been first treated with a combination of a halogen-containing titanium metal compound selected from titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium oxybromide and trichlorotitanium ethoxide, and at least one halogen-containing non-titanium metal selected from Hf, Zr and Sc, optionally in presence of a polar liquid medium and an electron donor, and then treated one or more times with one of said halogen-containing titanium metal compound, halogen-containing non-titanium metal compound or a combination thereof, solids being isolated between said treatments. 2. Solid catalyst component according to claim 1, characterized in that the halogen-containing titanium metal compounds and non-titanium metal compounds are selected from the halides, oxyhalides, C^-C^2 alkoxyhalides, hydridohalides and C^-C^2 alkylhalides of Ti, Zr and Hf. 3. Solid catalyst component according to claim 1, characterized in that the halogen-containing titanium metal compounds and non-titanium metal compounds are selected from chlorides of Ti, Zr and Hf. 4. Solid catalyst component according to claim 1, characterized in that the titanium and non-titanium metal compounds are present in total in an amount of from 5 to 100 mol per moles of MgC^. 5 . Process for the production of a solid catalyst component, characterized in that it essentially consists of treating an activated, anhydrous MgCl2/alcohol adduct, in an inert atmosphere, first with a combination of a halogen-containing titanium metal compound selected from titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium oxybromide and trichlorotitanium ethoxide, and at least one halogen-containing non-titanium metal selected from Hf, Zr and Sc, optionally in the presence of a polar liquid medium and of an electron donor, and then treatment one or more times with one of said halogen-containing titanium metal compounds, halogen-containing non-titanium metal compounds or a combination thereof, initially at 0°C and then at a temperature from 30 to 120°C for a time period from 30 to 240 minutes for each treatment, solids being isolated between treatments. 6. Method according to claim 5, characterized in that the metal in the halogen-containing non-titanium metal compound is selected from Zr and Hf. 7. Method according to claim 5, characterized in that the activated anhydrous MgCl2 is treated with a halogen-containing titanium compound, and at least one halogen-containing, non-titanium metal compound, and then with the halogen-containing titanium compound alone or in combination with the same or a different halogen-containing non-titanium metal compound. 8. Method according to claim 5, characterized in that the anhydrous MgCl2 is treated with a halogen-containing titanium compound, and at least one halogen-containing non-titanium metal compound, then with at least one halogen-containing, non-titanium metal compound alone or in combination with a halogen-containing titanium metal compound, and then with the same or a different halogen-containing non-titanium metal compound as used in the immediately preceding treatment. 9. Use of the solid catalyst component according to claims 1-4 together with an organometallic compound as an activator, optionally with an electron donor, for the polymerization of alpha-olefins. 10. Use according to claim 9, comprising polymerization of at least one alpha-olefin monomer of the formula CH2=CHE where R is a Cl-C12 branched or straight chain alkyl or unsubstituted or substituted cycloalkyl in the presence of an inert hydrocarbon solvent and the catalyst component according to claim 2 by a temperature in the range 50-80°C for 1-4 hours, and recovery of the resulting polymer.